Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3
2 Polarization Modulation Infrared Reflection Absorption
Spectroscopy: From Theory to Experiment . . . . . . . . . . . . . . . . . . . .
7
2.1 Propagation of Infrared Radiation in a Medium and Its Reflection
and Transmission at Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . .
7
2.2 Application of IRRAS to the Electrochemical Interface . . . . . . . . . 13
2.3 Experimental Considerations Prior to In Situ
Spectroelectrochemical Experiments . . . . . . . . . . . . . . . . . . . . . . 21
2.3.1 Selection of the Mirror (Electrode) Material . . . . . . . . . . . . 21
2.3.2 Selection of the Optical Window Material . . . . . . . . . . . . . 24
2.3.3 Composition of the Sample: Isotopic Substitution
in IRS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.4 Polarization Modulation Infrared Reflection-Absorption
Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3 In Situ PM IRRAS Studies of Redox-Inactive Molecular Films
Adsorbed on Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.1 Adsorption of Inorganic Ions on Metal Electrode Surfaces:
First Application of PM IRRAS with Electrochemical Control . . . . 47
3.2 Determination of Potential-Driven Structural Changes
in Films of Amphiphilic Molecules: In Situ PM IRRAS . . . . . . . . 49
3.3 In Situ PM IRRAS Studies of Films of Biomolecules
Adsorbed on Electrode Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3.1 Determination of Potential-Driven Structural Changes
in Lipid Bilayers: In Situ PM IRRAS . . . . . . . . . . . . . . . . 55
3.3.2 Determination of Potential-Driven Structural Changes
in Models of Cell Membranes Interacting with Small
Molecules: In Situ PM IRRAS . . . . . . . . . . . . . . . . . . . . . 68
ix
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3
2 Polarization Modulation Infrared Reflection Absorption
Spectroscopy: From Theory to Experiment . . . . . . . . . . . . . . . . . . . .
7
2.1 Propagation of Infrared Radiation in a Medium and Its Reflection
and Transmission at Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . .
7
2.2 Application of IRRAS to the Electrochemical Interface . . . . . . . . . 13
2.3 Experimental Considerations Prior to In Situ
Spectroelectrochemical Experiments . . . . . . . . . . . . . . . . . . . . . . 21
2.3.1 Selection of the Mirror (Electrode) Material . . . . . . . . . . . . 21
2.3.2 Selection of the Optical Window Material . . . . . . . . . . . . . 24
2.3.3 Composition of the Sample: Isotopic Substitution
in IRS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.4 Polarization Modulation Infrared Reflection-Absorption
Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3 In Situ PM IRRAS Studies of Redox-Inactive Molecular Films
Adsorbed on Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.1 Adsorption of Inorganic Ions on Metal Electrode Surfaces:
First Application of PM IRRAS with Electrochemical Control . . . . 47
3.2 Determination of Potential-Driven Structural Changes
in Films of Amphiphilic Molecules: In Situ PM IRRAS . . . . . . . . 49
3.3 In Situ PM IRRAS Studies of Films of Biomolecules
Adsorbed on Electrode Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3.1 Determination of Potential-Driven Structural Changes
in Lipid Bilayers: In Situ PM IRRAS . . . . . . . . . . . . . . . . 55
3.3.2 Determination of Potential-Driven Structural Changes
in Models of Cell Membranes Interacting with Small
Molecules: In Situ PM IRRAS . . . . . . . . . . . . . . . . . . . . . 68
ix